Reactive dyestuffs



United States Patent Ofiiice 3,133,911 REACTIVE DYESTUFFS Hans-Rudolf Byland, Riehen, and Hans Ischer, Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland No Drawing. Filed May 23, 1960, Ser. No. 31,214 May 22, 1959 Claims priority, application Switzerland Claims. (Cl. 260-454) This invention relates to reactive dyestufifs of the for- A represents the radical of a compound which contains at least one substituent that can be readily split off as an anion and/ or a C-C multiple linkage capable of addition, and

Cp represents the radical of a coupling component of the naphthalene series and the nucleus B may contain further substituents.

The process for the production of the new reactive dyestuffs consists in reacting 1 mole of a compound which is condensible with a substance containing an exchangeable hydrogen atom and contains at least one substituent which can be readily split off as an anion and/ or a CC multiple linkage capable of addition, with 1 mole of an aminoazo dyestuif of the general formula CH3 SIO H S OaH (3113 (II) wherein Cp the aforecited meaning and the nucleus B may be further substituted.

The aminoazo dyestufl of Formula II used as starting product is obtained by coupling the tetraz o compound of i 1 mole of 4,4'-diarnino-5,5-di1nethyl-1,l-dipheny1-2,2-disulfonic acid with 1' mole of a coupling component of the naphthalene series and with 1 mole of an aminobenzene which couples in para position to the amino group and may contain further substituents.

Examples of suitable coupling componentsof the naphthalene series based upon the radical Cp are hydroxynaphthalenemono-, -dior -trisulfonic acids such as l-hydroxynaphthalene-4- or -5-sulfonic acid, Z-hydroxynaphthalene-4-, -6-, -7- or -8-sulfonic acid, l-hydroxynaphthalene-3,6-, -4,6-, -4,7- or -4,8-disulfonic acid, 2-hydroxynaphthalene-3,6- and -6,8-disulfonic acid, l-hydroxyand -2-hydroxynaphthalene-3,6,8-trisulfonic acid and their mixtures, 2-hydroxynaphthalene, aminohydroxynaphthalenemonoand -disulfonic acids and their N-acyl, N-alkyl and N-aryl derivatives such as Z-amino-S-hydroxynaph thalene-6-sulfonic acid, Z-amin'o-S-hydr0xynaphthalene-3, 6-disulfonic acid, Z-amino-5-hydroxy-naphthalene-7-sultonic acid, Z-amino-S-hydroxynaphthalene-1,7-disu1fonic acid, 1-arnino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-arnino-S-hydroxynaphthalene 2,4 disulfonic acid, 1- amino-8-hydroxynaphthalene-4,6-disulfonic acid, 1,8-dihydroxynaphthalene 3,6 disulfonic acid, 1 amino-8-hydroxynaphthalene-4-sulfonic acid, l-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-arnino-6-hydroxynaphthalene-8-sulfonic acid, Z-acetylamino-S-hydroxynaphthalene- 7-su1fonic acid, l-benzoylamino 8 hydroxynaphthalene- 3,6-disulfonic acid, 2-(2'-4',6'-trimethyl)-phenylamino-8- hydroxynaphthalene-6-sulfonic acid, 2-phenylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-6- 3,133,911 Patented May 19, 1964 or 7-sulfonic acid, 2-niethylaminonaphthalene-6- or -7-sulfonic acid, 2-(4'-methoxy)-phenylamino-5-hydrox3u1aphthalene 7 sulfonic acid, Z-N-carbomethoXyamino-S-hydroxynaphthalene 1,7 disulfonic acid, 2-chloroacetylamino-8-hydroxynaphthalene-6-sulfonic acid, Z-fl-chloropropionylamino 5 hydroxynaphthalene-7-sultonic acid, l-(4,6'-dichloro l',3',5 triazinyl (2') amino)-8-hydroxynaphthalene-3,6-disulfonic acid, 2- (4',6'-dichloropyrimidyl-(2')-amino) 5 hydroxynaphthalene-1,7-disulfonic acid and -7-monosulfonic acid.

I Important aminobenzenes are e.g. aminobenzene, 1- amino-2- or -3-methylbenzene, 1-amino-3-acetylaminobenzene, l-amino 2,5 dimethoxybenzene, 1-amino-5- methyl-Z-methoxybenzne, 1-arnino-3-propionylor butyrylaminobenzene, 1,3-dia'minobenzene, 1-amino-2,5-dimethylbenzene, l-amino-2,B-tetramethylenebenzene.

The substituent A is preferably the radical of an acid containing at' least one mobile halogen atom and/or a C-C multiple linkage capable of addition, e.g. the radical of chloroacetic, bromoacetic, fi-chloroand S-bromopropionic, propiolic, acrylic, methacrylic, oc-ChlOlO-, fi-chloro-, a-bromoand B-bromoacrylic, 0:,[3- and 6,;3-dichloroor -dibromoacrylic, trichloroor tribromoacrylic, crotonic, rx-, 5, 'y-chlorocrotonic, oc, ,8-, 'y-bromocrotonic, ac-, /3-dichlorocrotonic, maleic, monochloroand monobromomaleic, dichloroand dibromomaleic, fumaric, monochloroand monobromofumaric, dichloroand dibromofumaric acid, fumaric acid monoester, dichloroand dibromosuccinic acid, or the radical of one of the following heterocyclic compounds: cyanuric chloride, cyanuric bromide, tetrameric cyanogen chloride or bromide, primary condensation products of the cyanuric chloride of the composition wherein Y stands for the radical, which may be further substituted, of a primary or secondary aliphatic alicyclic, aromatic, or heterocyclic amine, an aliphatic, alicyclic, aromrnatic or heterocyclic hydroxy or thiol compound, in particular the radical of aniline, its alkyl and sulfonic acid or carboxylic acid derivatives, low monoand dialkylamines, or the radical of ammonia; further 2,4,6-trichloropyrimidine and 2,4,6-tribromopyrimidine, their deriavtives which carry in the 5-position the following substituents, e.g.' methyl, ethyl, carboxylic acid or sulfonic acid amide which may be substituted on the nitrogen atom, carboxylic acid methyl or ethyl ester, acyl, e.g. benzoyl, alkylene, e.g. allyl, chlorovinyl, substituted alkyl, e.g. carboxymethyl, chloroor bromoethyl, a methylene group between two pyrimidine nuclei, 2,4,5,6-tetrachloroor tetrabromopyrimidine, 2,6-dichloroor -dibromopyrimidine-4- carboxylic acid ethyl ester, 2,4,5-trichloropyrimidine, 2,6- dichloroor -dibromopyrimidine-4- or -S-carboxylic acid amide or sulfonic acid amide which may be substituted on the nitrogen atom, 2,5,6-trichloro-4-methyl-pyrimidine, 2,4-dichloro-5-chloromethyl 6 rnethylpyrimidine, 2,6-dichloro-4-trichloromethylpyrimidine. The substituent A can also be a diaryloxycyanuric radical, an arylur'ethane radical, an arylsulfonic acid alkyl radical, a sulfuric acid alkyl radical, an epoxy radical, a B-chloroor B-bromoethyl radical.

The simplest method of introducing the acid radicals is to employ the corresponding acid halides or, in certain cases, the acid anhydrides. The reaction is carried out preferably at low temperatures, eg O-20 C., and in presence of an acid-binding agent such as sodium carbonate, sodium hydroxide, calcium hydroxide or sodium 3 acetate, at a weakly acid, neutral or weakly alkaline reaction, e.g. in the pH region of 4 to 9. To bring about acylation, the carboxylic acid chloride, either as such or dissolved in two to five times its amount of benzene, chlorobenzene, methylbenzene, dimethylbenzene or acetone, is added dropwise to the aqueous, well buffered solution of the substance containing the amino group, at a temperature of e.g. 25 C. Acylation with the anhydrides can be accomplished in the same way. The introduction of a cyanuric radical is best effected in aqueous medium at about C. and at a weakly acid reaction, e.g. at pH values between 3 and 5.

Cyanuric chloride is employed as such in solid form or dissolved in an organic solvent, e.g. acetone. In the case of the primary condensation products of a cyanuric halide it is best to choose a temperature between 30 and 60 C. and a pH value of 4 to 6, while for the di-, triand tetrahalogenopyrimidines the temperature range of 40 to 100 C. is the most suitable, the pH region being preferably between 3 and 9.

On completion of condensation or coupling, the solution or suspension may be neutralized if desired and the final reactive dyestuff is salted out with sodium or potassium chloride or precipitated with acid. It is then filtered with suction, washed and dried.

The reactive dyestuffs of this invention are suitable, according to their constitution, for the dyeing, padding and printing of fibers of animal origin, e.g. wool and silk; synthetic polyamide fibers, e.g. nylon; leather; cellulosic fibers, e.g. cotton, hemp, linen; regenerated cellulosic fibers, e.g. viscose and cuprammonium rayon and mixtures of these fibers. The optimum conditions vary with the fiber and the dyestuff used. Animal fibers and synthetic polyamide fibers are dyed and printed or fixed in an acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. Dyeing can also be carried out in the acetic acid to neutral region in presence of leveling agents, e.g. polyoxethylated fatty amines or mixtures of these and alkylpolyglycol ethers, and the bath brought to a neutral or weakly alkaline reaction at the end of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate, soda etc. or compounds which react alkaline on heating, e.g. hexamethylene tetramine, urea.

The dyed goods are then thoroughly rinsed and soured with a little acetic acid if necessary.

Application of the dyestuffs to cellulosic fibers by dyeing, padding and printing techniques is carried out to best advantage in an alkaline medium, e.g. in presence of sodium carbonate or bicarbonate, sodium hydroxide or potassium hydroxide solution, sodium metasilicate, sodium borate, trisodium phosphate, ammonia, etc. To preclude reduction elfects in dyeing, padding or printing it is often an advantage to add a mild oxidizing agent, e.g. sodium 1-nitrobenzene-3-sulfonate. Generally the dyestuffs are fixed on cellulosic fibers by heat treatment. Depending on the reactivity of the reactive groups, a number of thedyestuffs can be dyed or fixed at low temperatures, e.g. 20-40 C.

The dyeings and prints obtained on cellulosic fibers are characterized by their outstanding fastness to wet agencies, which results from the formation of a stable chemical linkage between the dyestuff molecule and the cellulose molecule. In many cases the entire amount of applied dyestuff does not take part in the chemical reaction with the fiber; the unreacted portion of the dyestuif is then removed from the fiber by suitable operations such as washing and/ or soaping, if necessary at high temperatures. For this purpose synthetic detergents may be used, e.g. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate, monoand dialkylphenolpolyglycol ethers. The dyeings on wool possess excellent fastness to light, perspiration, water, sea water, milling, crocking and dry cleaning, and a number of the dyestuffs show good dyeing properties on this fiber.

The dyeings on cellulose fibers possess excellent fastness to light, water, sea water, washing, perspiration, crocking alkali and dry cleaning.

The dyestuffs reserve acetate, triacetate and polyethylene terephthalate fibers.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

Example 1 18.6 parts of 4,4'-diamino-5,5'-dimethyl-1,l-diphenyl- 2,2'-disulfonic acid are dissolved in 50 parts of water with the addition of about 13.6 parts of 30% sodium hydroxide solution. After the addition of 6.9 parts of sodium nitrite the solution, at 0-15", is run into a solution of parts of sodium chloride and 27 parts of 30% hydrochloric acid in 200 parts of water. To the tetrazo compound is added a solution of 12.3 parts of l-hydroxynaphthalene-4-sulfonic acid in 70 parts of water, followed by parts of finely crushed ice. Over the next 3 hours a solution of 14.8 parts of crystallized sodium acetate in 15 parts of water is dropped in. The coupling mass is stirred overnight at 0 and next morning it is rendered weakly alkaline by the addition of sodium carbonate. After stirring for some time the suspension is brought to pH 5 with dilute acetic acid, and 4.8 parts of l-amino-3- methylbenzene are added. Stirring is continued for about 10 hours, after which time sodium hydroxide solution is run in to make the solution weakly alkaline. It is then treated with a mixture of 3 parts of blood charcoal and 3 parts of infusorial earth. After filtration, the amonodisazo dyestuff formed is precipitated by acidification with 30% hydrochloric acid and filtered off.

The filter cake is dissolved in 250 parts of water at 60 and the solution adjusted to pH 4-5. After the addition of 9.2 parts of 2,4,6-trichloropyrimidine the mass is stirred for 4 hours at 60-65, during which time dilute sodium carbonate solution is dropped in to maintain the pH value between 4 and 5. On completion of the reaction the solution is treated with blood charcoal. After the solution has been clarified by filtration, sodium chloride is added, causing the dyestuif to be precipitated. It is filtered with suction, and the press cake washed with sodium chloride solution and dried. On grinding the dyestuff is obtained as a red powder which dissolves in water to give yellow-red solutions.

A mercerized cotton fabric is printed with a paste of the following composition:

30 parts of above-described dyestuif,

100 parts of urea,

385 parts of water,

450 parts of 4% sodium alginate thickening,

10 parts of sodium 1-nitrobenzene-3-sulfonate, 25 parts of sodium carbonate.

1000 parts The print is dried and fixed by steaming for 10 minutes. It is then rinsed with cold and again with hot water, soaped at the boil if necessary, given a further hot and cold rinse and dried. The print is of brilliant scarlet shade and possesses excellent fastness to wet treatments and good fastness to light.

In place of the 4.8 parts of 1-amino-3-1nethylbenzene used in this example, the equivalent amount of one of the following aminobenzenes: aminobenzene, 1-amino-2- methylbenzene, l amino 3 acetylamino-, -3-propionylaminoor -3-butyrylaminobenzene, 1-arnino-2,5-dimethylor -2,5-dimethoxybenzene, l-arnino-Z-methoxy-S-methylbenzene, 1,3-diarninobenzene or 1-amino-2,3-tetramethylene-benzene may be employed and the same procedure followed to give scarlet dyestuffs with very similar properties.

Example 2 76.8 parts of the disazo dyestufi? obtained by tetrazotization of 1 mole of 4,4-diamino-S,5-dimethyl-1,1'-diphenyl-2,2'-disulfonic acid and subsequent coupling with 1 mole of 1-hydroxy-naphthalene-4-sulfonic acid and 1 mole of 1-acetylamino-3-aminobenzene, are dissolved in 2500 parts of water. acylated by gradual addition of 11.3 parts of chlordacetyl chloride with stirring. At the same time sodium" bicarbonate is strewn in to maintain the pH of the solution between 5 and 7. When all the chloroacetyl chloride has been added, stirring is continued for 12 hours at the same' temperature and, if the reaction is not yet completed, a little more chloroacetyl chloride is added. As soon as no free amino group is indicated, the reaction mass is neutralized with sodium carbonate solution and the new dyestuff salted out with sodium chloride, isolated and dried at low temperature. It is a red powder which dissolves in Water with a clear red coloration. Applied to The solution is cooled to 0-5 and 6 chloride or 15.6 parts of chloroformic acid phenyl ester or 9 parts of acrylic acid chloride or 13.2 parts of monochloromaleic acid anhydride are used, dyestuffs with very similar properties are obtained.

Example 3' chloroacetic acid, 5 0 parts of sulfuric acid monohydrate and parts of oleum so that the temperature of 40 is not exceded. At the same time parts of oleum wool from an acetic acid bath, to which a wetting agent 65% are run 1n slowly. The mass is stirred for 12-15 may be added if desired, it gives brilliant scarlet'dyelngs" hours at room temperature. On' the following morning,

which are outstandingly level and have excellent wet no further free amino group being indicated, it is poured fastness and very good light fastness. onto ice and the precipitated dyestuif filtered off. The

2 parts 0f t abQVe deSCflbed dyestllfi, -8 part of an 20 dyestuiT is stirred into 2000 parts of cold water, neuoxethylated fatty amine and 0.5 part of an oleylpolyglycol tralized with 20% sodium carbonate solution, and the preether are dissolved m 5000 parts of water, and 2 part cipitated sodium salt of the dyestufi is salted out, filtered ofglacial acetic acid are added to the solution. ThlS' ff d d i d t l temperature i h vacuum dyebath 1S heatfid to 9 P A red powder is obtained'which dissolves in water with the bath Pmught t0 the boil In 30 lrflnutes- It 5 a scarlet coloration and dyes wool and polyamide fibers,

for 145 min tgs a f W001 g ll fii a i f i A if necessary with the addition of a'wetting agent, in level i F fi i g :521 52 a z g 3:2 shades of very good light and Wet fastness.

1S 0 mac p y g y The following table contains further dyestufis of be neutralized with ammonia and the goods treated m it Formula I characterized b the reactive radic I A th for 20 minutes at in order to obtain somewhat better 30 on y a e wet fastness. The same effect can be obtained by aftergr p treatment of the dyed goods in a fresh bath of 5000 parts H N of water and 3 parts of hexamethylene tetramine for 20-30 3 minutes at 9095.

When in place of the 11.3 parts of chloroacetyl chloride the CQITIPOlmd ffofll Whlch P 15 Clem/ed and the ade o in the above example, 12.6 parts of fl-chloropropionyl he aq e s l lon 1n olumns (I) to (IV).

(I) (II) (III) (IV) Example Shade Of the No. Reactive radical A HzN B D= Radical of aqueous solution 4 4,5,vtrichloropyrimidyl-(2) 4-amino-phenyl-(1) ly r xy naphthalene-tsulfonic acid. Scarlet,

5 do 4-amino-2rmethyl-phenyl-(1). d0 D0. 4-amino-2,5dimethyl-phenyl-(l) Do. 4-an1ino-2-acetyl-aminophenyl-(1); D0 4amino-3-methy1aminophenyl-(1) 4-amino-3-methoxy-dmethyl-phenyl-(1) D0 4-an1ino-2propionylamino-phenyl-(1) Do. 1-am1'no-2-butyry1amino-pheny1-(1) "do D 4-amino-2-rnethy1pheny1-(1) 1 hy roxy naphthalene 4,6 disul- D0.

ionic. acid. 4-aminophenyl-(1) 1O Do. 4-amino-2-acety1-amin0phe11yl'( 1) 0 Do. 4-amiuo-2-methyl-phenyl-(1) 1 hydroxynaphthalene 3,6 disul- Do.

tonic acid. 1 hydroxynaphthalene 3,6,8 tri- D0.

sulfonic acid. 2-hydroxynaphthalene-fi-sulfonic acid- Yellow-red. 2-hydroxynapl1thalene-4-su1t0nic acid- D0. 2-hydroxynaphthalene-B-sulfonie acid- Do. l-hydroxynaphthalene-5-su1tonie acid- Scarlet. 2 h sadroxynaphthalene 6,8 disulfonie Yellow-red.

E101 1 hyidroxynaphthalene 4,7 disulfonic Scarlet.

aCl do 1 hyidroxynaphthalene 4,8 disulfonie Do.

301 fi-Chloropropionyl 4-amino-2-methylphenyl-(1) l-hydroxynaphthalenel-sulfonic acid Do. Acrylyl... .d0 d0 Do. B-Chloroacrylyl. do 7 .d0 Do. Bfi-DichloroaerylyL do -do D0. Trichloroacrylyl do do Do. B-Ch1orocrotouyl do .-d0 Do.

4-ch1oromethy1benzoyl 4,6-dichloro-1,3,6-triazinyl-(2) 4-chloro-6-amino-1,3,5-triaziny (2) 4-chlor0-6-(4-sulfophenylamino)-1,3,

triazinyl-(Z).

35 4,6-disu1fur0usester-1,3,5-triaziny1-(2) 36- 3-chloro-2-hydroxypropyl 271 4,5-diichloropyrimidyl- (2) 41 4,6-dibromopyrimidyl-(2) 42 4,5,6-trlbromopyrimidyl-(2)- (I) (II) (III) (IV) Example Shade of the No. Reactive radical A HzN B Cp=Radica1 01- aqueous solution 43 Ghloroacetyl 4-amino-2-mcthylphenyl-(I) 1-hyddroxynaphthalene-4,G-disulfonic Do.

aci n 1-hydroxynaphthaleno-5-su1ionic acid Do. 4amino-2-aeetylamino-phenyl-(1) do Do. d o 1-hydr0xynaphthalcnc-4,8-suli0nio acid Do. 47.- do 4-am1no-2 ch1oroacetylammo-phcnyl 1-hydroxynaphthalenc-S-sulionicacid. Do. 48 B-Chloroproplonyl 4411511111oilfiachloropropionyl-amino- 1-hydr0xynaphthalene-4-sulionicacid.. D0.

p eny- 49 4,6-dichloropyrimidyl-(2) 4-amino-2-methylphenyl-(1) 2-amino-8-hydr0xynaphthalene-fi-sul- Blue-red.

fonic acid (acid coupled). 50 4,5,6-tnchlropyrtmldyl-(2) 2-(2,4,6-trimethyl-phenylamln0)-8- Bluish hydroxynaphthalene-S-sulfonic acid Bordeaux. (acid coupled). 51 Chloroacetyl" 2-acetyl-amino-5-hydroxynaphthalcne- Red.

7-sulfonic acid. l-bcnzoylamino-8hydroxynaphthalcue- Blue-red.

3,6-disulfonic acid. 2-chloroacctylamino-E-hydroxynaphtha- Red. lcne-1,7-disulfonic acid. 4,G-dichloro-l,3,5-triazmyl-(2) -.d0 2-[4-ohloro-6-phenylamino-1,3,5'-tri- Blue-red.

azinyl-(2)-amino]-5-hydr0xynaphthalene-7,4-disulf0nio acid. 55 Ohloroaoetyl 4-amino-2,3-tetramethylene-phenyl-(1) 1-hydroxynaphthaleneA-sulfonlc aoid Red. 56 .do 4-am1no-2-methylphenyl-(l) do Scarlet.

Example 57 A fabric of viscose staple fibre is padded with a 3% neutral solution of the dyestuff of Example at 50 to give an increase of about 85% over the dry weight. After intermediate drying, the dyestuif is fixed by treating the goods for about 1 hour with constant agitation in a bath at 8090 containing 250 parts of calcined sodium sulfate, parts of trisodium phosphate and 3 parts of sodium 1-nitrobenzene-3-sulfonate per 1000 parts of liquor. The liquor-to-goods ratio of this fixation bath is between 1:10 and 1:50. After fixation, the goods are well rinsed with cold water, soaped at the boil, rinsed and dried. The scarlet shade obtained is outstandingly fast to light and wet treatments.

liquor containing 40 g./l. of calcined sodium carbonate, 20 g./l. of the dyestuff of Example 7, and 5 g./l. of sodium 1-nitrobenzene-3-sulfonate. The padding effect gives an increase of 80100% on the dry weight. The fabric is rolled and conditioned in a chamber for 4 to 6 hours at 90-95 and at constant humidity then Well rinsed in cold and warm water, soaped at the boil with 5 g./l. of soap for 15 minutes, rinsed again and dried. A scarlet dyeing with good light and wet fastness is obtained. The

treatment in a conditioning chamber can also be replaced by steaming for 10 to 15 minutes at l02104 or by a treatment in dry heat for 4-5 minutes at 140-150 of for 12 minutes at 180-200.

Example 58 Formulae of representative dyes of the foregoing A mercerized cotton fabric is padded at with a 40 examples are as follows.

Example 1:

c1 5 0 3 S0311 OH i i Cl-O O-EN N=N OH; 11 CH Example 2:

CH; S0 13. OH Cl-OHr-CO-HN C N=N-C N=:N

NH-COCH3 SOaH CH3 Example 3:

0113 S0313. 0H o1-o11,-oo-HNQN=NQ N=N BITE 503E: CH3

00H 1 C 20 SOZH Example 4: 01

(ll-C 9 1 Example OH S0 H 0H 01 \III a I a I o1c CHN-N=N N=N N I I OH: SOQH CH3 S0 11 Example 12:

01 (I CH3 303K I V 7 OH 01 III c1 o CHNON= N=N N l I OH] SO3H CH3 SOQH SO3H Example 5 6:

(EH3 SOaH OH 01-0 H2-o OHNN=NQN=N (EH3 03H CIHS SO3H Having thus disclosed the invention what we claim methylpyrimidyl (2), 4,6 dibromopyrimidyl-(Z), i 4,5,6 tribromopyrimidyl (2), 4,6 dichloropyrim- 1. Reactive dyes of the formula I idyl (2), 4,5,6 trichloropyrimidyl (2), and

cm 303E 4-chloro-6-amino-1,3,5-triazinyl-(2).

I Cp represents the radical of a coupling component selected from the group consisting of a hydroxy- A N G naphthalene monosulfomc acid, a hydroxynaphtha- I y SOBH 5 lene disulfonic acid, a hydroxynaphthalenetrisulfonic acid, a (trimethylphenyl)-amino-hydroxynaphthawherein lene-sulfonic acid and an acylaminohydroxynaphtha- A represents a radical capable of reacting with cellenedisulfonic acid.

lulosic and polyamide fibers, said radical being sex represents a member selected from the group conlected from the group consisting of chloroacetyl, sisting of hydrogen, methyl, methoxy and together 5 chloropropionyl, 4,5,6 trichloropyrimidyl-(Z), with y, the chain CH CH CH CH acrylyl, fl-chloroacrylyl, 13,;8-dichloroacrylyl, trichloy represents a member selected from the group conroacrylyl, p-chlorocrotonyl, 4-chloromethylbenzoyl, sisting of hydrogen, methyl, methoxy, amino, lower 4,6dichloro-1,3,5-triazinyl-(2), 4-chloro-6-(4-sulfoalkanoyl amino and, together with x, the chain phenylamino) 1,3,5 triazinyl-(Z), 3-chloro-2-hy- -CH CH CH -CH droxypropyl, 4,5 dichloropyrimidyl-(Z), 4,5 diand z represents a member selected from the group chloro 6 methyl-pyrimidyl (2), 4,5-dibromo-6- consisting of hydrogen, methyl and methoxy.

2. The reactive dye of the formula 0H so H OH O1(6/ If I a a I 50 K CH3 SO H 3. The reactive dye of the formula 01 A CH: 0311 OH cl-fi III I l 4. The reactive dye of the formula $1 0 OH: 80311 OH 1 01-0 c-HN N=N N= CH, 50.11 CH: SOIH 5. The reactive dye of the formula CH] S0311 OH OI OH, CO HN N=NQQ N= CH: 50:11 CH:

6. The reactive dye of the formula 011, 50,3 011 c1-oH,-co-HNQ-N=NC N=N I NH-OO-CH| son?! OH,

References Cited in the file of this patent UNITED STATES PATENTS Haller et a1. Nov. 8, 1932 Heslop et a1. May 3, 1960 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,133,911 May 19, 1964 Hans-Rudolf Byland et a1. It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patentshould read as corrected below Column 1, lines 33 to 38, the right-hand portion of formula (II) for "-N=NC"' read N=NCp column 2, line 44, for "arommatic" read aromatic column 5, line 27, for

"dyening" read dyeing Signed and sealed this 24th day of November 1964.

(SEAL) Attest:

EDWARD J. BRENNER ERNEST W. SWIDER Commissioner of Patents A I testing Officer 

1. REACTIVE DYES OF THE FORMULA 